JPS6344822B2 - - Google Patents
Info
- Publication number
- JPS6344822B2 JPS6344822B2 JP54139727A JP13972779A JPS6344822B2 JP S6344822 B2 JPS6344822 B2 JP S6344822B2 JP 54139727 A JP54139727 A JP 54139727A JP 13972779 A JP13972779 A JP 13972779A JP S6344822 B2 JPS6344822 B2 JP S6344822B2
- Authority
- JP
- Japan
- Prior art keywords
- ions
- complexing agent
- plating
- copper
- item
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000007747 plating Methods 0.000 claims description 79
- 239000010949 copper Substances 0.000 claims description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 69
- 229910052802 copper Inorganic materials 0.000 claims description 69
- 239000008139 complexing agent Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 24
- 229910001453 nickel ion Inorganic materials 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- -1 hypophosphite ions Chemical class 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 14
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 11
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000001261 hydroxy acids Chemical class 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical class OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims 1
- 150000003893 lactate salts Chemical class 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 51
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 45
- 239000003638 chemical reducing agent Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 18
- 238000000151 deposition Methods 0.000 description 17
- 230000008021 deposition Effects 0.000 description 16
- 238000007772 electroless plating Methods 0.000 description 16
- 229910052759 nickel Inorganic materials 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 229910017052 cobalt Inorganic materials 0.000 description 11
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 5
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000006259 organic additive Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005844 autocatalytic reaction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- ZMLDXWLZKKZVSS-UHFFFAOYSA-N palladium tin Chemical compound [Pd].[Sn] ZMLDXWLZKKZVSS-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- VGVLFMIJNWWPBR-UHFFFAOYSA-N 2,2,3-trihydroxypentanedioic acid Chemical compound OC(=O)CC(O)C(O)(O)C(O)=O VGVLFMIJNWWPBR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NPTTZSYLTYJCPR-UHFFFAOYSA-N Trihydroxy-glutarsaeure Natural products OC(=O)C(O)C(O)C(O)C(O)=O NPTTZSYLTYJCPR-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Description
本発明は銅の無電解メツキに関し、本願の譲受
人に譲渡されている1978年５月25日出願の米国特
許第4209331号明細書に記載された発明に対する
特定の改良を与えるものである。特に、本発明
は、非ホルムアルデヒド型還元剤を用い、ニツケ
ル又はコバルトイオンの存在下で溶液に溶けてい
る銅イオンを金属銅に還元してその溶液に接触し
ている適当に調整した基材上に、従来得られてい
た限られた厚みより厚い希望の厚さをもつ金属付
着物又は被覆を連続的メツキ工程として形成する
銅の無電解メツキに関する。ここで用いる無電解
メツキという言葉は、メツキの厚さが最初のメツ
キ速度と同じ実質的に同じ速度で時間と共に増大
するメツキ操作を意味する。
上述の米国特許第4209331号明細書には、商業
的設備の無電解メツキ浴中で、銅イオン還元剤と
して非ホルムアルデヒド型還元剤を適切に用いる
ことができる発明が記載されているが、適当に調
製した基材、特に触媒処理した非導電性基材上に
導電性金属付着物或は被膜を生ずるのに或る限界
が観察されている。記載されている還元剤の中で
特に有用なのは次亜燐酸塩である。本発明はその
ような非ホルムアルデヒド型還元剤系で、メツキ
浴溶液中に自触媒剤としてニツケル又はコバルト
イオンを含有させることにより連続的にメツキさ
れた希望の厚さの金属銅を与えることにある。
従来技術
上述の米国特許第4209331号明細書に含まれて
いる従来技術についての記載は、参考のためここ
でも述べるが、種々の基材特に非導電性基材上に
銅を付着させるのに商業的に実施されている従来
の無電解メツキは、ほとんど例外なくロツシエル
塩、アミン類等々の如きよく知られた薬品で錯化
された二価銅イオンの高度にアルカリ性のホルム
アルデヒド溶液を用いていることを示している。
そこで論じられている従来法で教示されているこ
と及び経験を見れば、次亜燐酸塩の如き非ホルム
アルデヒド型還元剤が無電解メツキで銅イオンを
金属銅へ成功裡に還元することができ、然も典型
的なホルムアルデヒド系では得られない利点を与
えることができることは予期しない全く意外なこ
とであつた。
技術文献は明らかに次亜燐酸塩薬剤が無電解ニ
ツケルメツキ法で還元剤として効果的で広く用い
られていることを示しているが、ニツケル浴の次
亜燐酸塩を銅浴でのホルムアルデヒドの代りに用
いることができることは従来技術は示唆していな
い。例えば従来の特許では無電解ニツケル浴と銅
浴の両方が記載されている場合、浴の組成は必ず
銅配合物に対してはホルムアルデヒド型還元剤を
用いているのに対し、ニツケル配合物に対しては
次亜燐酸塩が用いられている。
最近の米国特許第4036651号には、アルカリ性
ホルムアルデヒド型無電解銅溶液に「メツキ速度
調節剤」として次亜燐酸ナトリウムを配合するこ
とが教示されている。その特許は「次亜燐酸ナト
リウムは、それ自身はニツケル、コバルト、パラ
ジウム及び銀の無電解メツキ浴の還元剤である
が、それはアルカリ性無電解銅メツキ浴に単独で
用いられた時には満足な還元剤ではない（即ち、
Cu++をCu0へ還元しない）」と明白に述べている。
その特許は記載されている浴を論じている所で、
次亜燐酸ナトリウムはメツキ反応では使い尽され
ることはないが、その代りホルムアルデヒド還元
の触媒として働くように見えると述べている。
米国特許第3716462号には、亜鉛又は亜鉛合金
物体上に、可溶性銅塩例えば硫酸銅、錯化剤例え
ばクエン酸、及び還元剤例えば次亜燐酸ナトリウ
から本質的になる無電解メツキ溶液を用いて銅の
被覆を形成することができることが述べられてい
る。しかし、その特許は「之迄、亜鉛又はその合
金に無電解銅メツキを適用することは困難で実施
できないと考えられてきたと述べているが、その
見解は亜鉛や鋼の如き基礎金属を銅含有溶液中に
浸漬することによつてメツキする容認された一般
的知識に反するものである。更にその特許は亜鉛
のメツキに限定されているが、無「電解メツキ」
は一般に非導電性基材上に金属被覆を付着させる
ことを指すものと一般的に考えられている。更に
その特許の溶液中に存在する次亜燐酸塩は記載の
メツキ法では本当には役に立たないと思われる。
本発明の概略
本発明は無電解銅付着用アルカリ性ホルムアル
デヒド型還元剤溶液に伴われる欠点を解決するの
みならず、更に非ホルムアルデヒド型還元剤銅メ
ツキ溶液を用いて従来得られていた厚さより大き
な種種の厚さの付着物を得ることができる利点を
与えるものである。即ち、本発明は非ホルムアル
デヒド型還元剤による無電解銅メツキ浴を用いた
時、最初のメツキ速度と同じ実的に一定の速度で
金属銅を連続的にメツキすることを与えるもので
ある。之は本発明によれば銅以外の金属イオン特
にニツケル又はコバルトイオンを非ホルムアルデ
ヒド型還元剤の外に含有する無電解銅メツキ浴を
与えることによつて達成される。
従つて本発明は、米国特許第4209331号明細書
に記載された新規な非ホルムアルデヒド還元剤に
よる無電解銅浴系の原理的利点のみならず、メツ
キ即ち付着が長い浸漬時間に対し限界のある厚さ
の付着物を生ずるのではなく、一層直線的な付着
速度を維持するという更に驚くべき予想外の主た
る利点をも与える。ニツケル又はコバルトイオン
は、連続的メツキを生ずるための非ホルムアルデ
ヒド還元系で相乗的効果を与える特徴をもつ。結
局本発明の無電解銅浴組成物及びメツキ法は、非
ホルムアルデヒド還元銅メツキ系を用いて一層厚
い付着物を得、商業的規模で一層広範囲の用途を
与えることができるようにする。
無電解銅メツキ浴中に異なつた成分を用いて異
なつた利点が得られることが発見されている。例
えば本発明の組成を用いた無電解銅メツキ浴に
は、第二銅イオン源及びそれらの溶剤を与える従
来の成分の外に、非ホルムアルデヒド型還元剤、
有利には次亜燐酸塩、コバルト又はニツケルのイ
オン源、及びニツケル又はコバルトのイオンとの
有利な適合性をもつように選択された錯化剤又は
その混合物を含むのが有利である。
本発明で有利に用いられる錯化剤又はその混合
物には、ニツケル又はコバルトが銅と共析できる
ようにするものが含まれる。特定の理論に束縛さ
れたくはないが、錯化剤がその条件に合うのは、
それらの薬剤を含む溶液中のニツケル又はコバル
トの安定定数が銅の安定定数と実質的に同じで、
同じ反応速度論的推進力が得られる場合であると
の理論付けがなされている。同様に、行われてい
る作用について特定の理論に束縛されたくはない
が、ここで述べていることは自触媒反応促進金属
と溶けている銅の両方に対する還元電位が実質的
に同じで共析を起すことができるということであ
る。
種々の錯化剤又はそれらの混合物が上述の希望
の特性を満すものと予想されるが、その特定の例
には種々のヒドロキシ酸及びそれらの金属塩、例
えば酒石酸塩、グルコン酸塩、グリセリン酸塩、
乳酸塩等々が含まれる。更に他のものでも制御さ
れた条件では成功裡に作用するであろう。それら
にはアミン型錯化剤、例えばＮ―ヒドロキシエチ
ル エチレンジアミン 三酢酸（HEEDTA）、
エチレンジアミン四酢酸（EDTA）及びニトリ
ロ三酢酸（NTA）及びそれらのアルカリ金属塩
が含まれる。金属浴系は任意に、不飽和有機化合
物添加剤を含んでいてもよく、例えばブチンジオ
ール又はブテンジオール、アルキルスルホン酸、
ナトリウム、及びポリオツクス（Polyox）（ユニ
オン・カーバイド社製ポリオキシエチレンオキサ
イド）、プルロニツク（Pluronic）77（BASF
Myandotte Chemical Co.製ポリオキシエチレン
―ポリオキシプロピレン ブロツク共重合体）を
含んでいてもよい。
コバルト又はニツケルイオンを含む無電解銅浴
はアルカリ条件に維持する。pHは一般に少なく
とも７以上、好ましくは11〜14の範囲、最適結果
を与える水準に維持されるべきである。なぜなら
それより低いpH水準では系は非連続的になり易
く、即ち限られた厚さ迄しかメツキできず、それ
は屡々限定的過ぎるからである。後で一層詳細に
説明するように、メツキ浴の性質及び工程因子例
えば浴安定性、付着速度及び付着物純度は、上述
の成分を適切に選択すること及びそれらの相対的
量の調節によつて決定するのが有利である。
従つて本発明の一態様は、ニツケル又はコバル
トイオンを含み、ホルムアルデヒドを含まない無
電解銅メツキ浴を与えることである。
本発明の他の態様は、ホルムアルデヒドを含ま
ない無電解銅メツキ浴を用いて銅を連続的にメツ
キする方法を与えることである。
本発明の更に他の態様は、ホルムアルデヒドを
含まない銅浴系に銅以外の金属イオンで、それら
イオン又はその存在により得られる析出物が銅付
着を連続的に行わせる触媒として働くような金属
イオンを配合することにより、その系で本質的に
金属銅を連続メツキさせるための無電解銅メツキ
浴組成物及びメツキ法を与えることである。
前述及び他の態様及び本発明の利点及び目的
は、その好ましい具体例についての次の記載から
更に明らかになるであろう。
好ましい具体例
本発明の組成を有するメツキ溶液は、溶媒、通
常水及び第二銅イオン源の如き従来の無電解銅浴
の主たる成分範疇に入るものの外に、錯化剤、非
ホルムアルデヒド型還元剤、この場合次亜燐酸塩
の可溶性源及びニツケル又はコバルトのイオン源
及び必要ならpH調節剤を含有している。
メツキ溶液中の銅、ニツケル及びコバルト源
は、それら金属の通常用いられる可溶性塩のいず
れかでよい。塩化物及び硫酸塩が入手し易いので
通常好ましいが、他の有機又は無機の陰イオンも
用いることができる。
メツキ浴の適当なpH水準は連続的メツキを得
るために重要であるが、アルカリ条件を維持する
ためのpH調節は必要であろう。もし調節が必要
ならば、その値を正しい操作範囲に戻すため更に
標準の酸又は塩基を用いてもよい。酸性メツキが
析出し続けていくと時間と共に浴のpHが低下す
るので、長い使用期間では、特にpHを好ましい
11〜14の範囲に維持することが必要になるであろ
う。通常、水酸化ナトリウムの如き苛性物質を添
加する。選択したpH範囲を維持する際の助剤と
して緩衝剤を用いてもよい。
本発明による満足すべき連続的析出物は、基材
としてその表面が適切に調製されたものを用いる
ことによつて得られる。即ち、非導電性基材は、
当分野で既知のパラジウム・錫触媒で触媒処理さ
れた表面を有する。ここに記載する系で、コバル
ト又はニツケルイオンの存在下で銅イオンが銅金
属に連続的に還元される機構は知られていない。
しかし、仮説として次のように考えられる。基材
の表面上にあるパラジウムの如き貴金属触媒が、
次亜燐酸還元剤から強い還元性ラジカル又はラジ
カルイオンを形成することにより反応を開始す
る。触媒表面上の之等強い還元性物質は、電子移
動反応により銅イオンを銅金属へ還元する働きを
する。銅金属の還元に伴なつて、少量の溶けてい
るコバルト又はニツケルも還元され、ニツケル金
属又はコバルト金属又は或る銅コバルト又は銅ニ
ツケル合金として銅析出物中に少量含有されるも
のと思われる。析出した金属を調べてみると、少
量のコバルト又はニツケルが銅析出物中に存在す
ることが判明している。付着が進行していくにつ
れてパラジウム貴金属触媒は結局被覆され、含有
されたコバルト又はニツケル金属、又はコバル
ト・銅或はニツケル銅合金が更に次亜燐酸塩還元
剤と反応し、無電解メツキ工程が継続するのに必
要な還元性ラジカル又はラジカルイオンを生ずる
ものと思われる。
次亜燐酸ナトリウムは次亜燐酸塩の最も入手し
易い形態のものであり、従つて好ましい。次亜燐
酸も入手でき、この材料の浴を調製するためpH
調節剤と共に用いることができる。最適濃度は合
理的時間内で適切な銅被膜が形成されるのに充分
な濃度である。
用いられる錯化剤の種類は、或る程度メツキ速
度の外、メツキの連続性及び得られる付着物の種
類に影響を与えるであろう。例えばコバルトが次
亜燐酸塩還元銅浴中の自触媒反応促進剤イオンで
ある場合、酒石酸塩、グルコン酸塩及びトリヒド
ロキシ グルタール酸の如き錯化剤が薄い被覆を
連続メツキするのに有利である。
Ｎ―ヒドロキシエチル エチレンジアミン 三
酢酸（HEEDTA）、エチレンジアミン四酢酸
（EDTA）或はニトリロ三酢酸（NTA）の如き
アルキルアミン錯化剤を用いた時、ニツケル又は
コバルトイオン含有銅浴系は、もし添加された錯
化剤の量が全てのニツケル又はコバルトイオンを
捕捉するには不充分であるならば連続的である。
即ち、いくらかのニツケルとコバルトイオンは連
続的メツキ工程を維持するために自由に共析でき
る状態になつていなければならない。ニツケルと
コバルトは、もし錯化剤が余りにも強過ぎると、
即ち一層高度の酸化状態の安定化を促進すると共
析しない。従つて系中のそのような錯化剤の均衡
が、連続的メツキを行うためには制御されなけれ
ばならない。
上記錯化剤の外に、不飽和有機化合物、重合
体、及びそれらの組み合せを添加してもうまくい
く。之等の任意的添加剤、例えばブチン又はブテ
ンジオール、アルキルスルホン酸ナトリウム及び
重合体例えばポリオツクス及びプルロニツク77は
本発明の系に適合し、電気メツキ系で知られてい
るのと同じような作用をそこで及ぼすであろう。
乃等無電解溶液からの銅の析出速度は、本質的
に直線的であることが観察されている。例えばメ
ツキは90分後でも依然として進行しており、この
事は析出が一層長く継続していることを示してい
る。なぜならそのような時迄に触媒処理された表
面上のパラジウムは析出物によつて被覆されてし
まつていることは確かであり、もはや連続的メツ
キ操作のための活性触媒としては作用しないから
である。この系は純粋の銅に対しては不活性であ
るように見えるが、之は最期不動態化を解決する
ように表面を適当に触媒処理することにより種々
のやり方で解決することができ、それによつて無
電解メツキが起きる。
次の実施例は本発明を実施するための好ましい
条件を例示している。
実施例 １−18
これらの実施例では、“Epoxgglass FR−４
PLADD Laminate”として商業的に知ら
れているグラスフアイバー補強エポキシ樹脂基材
にアルミニウム箔を結合させたものからなる積層
体素材の形に初めからなつているプラスチツク基
材である加工品を、米国特許第3620933号に記載
されたマクダーミツド・インコーポレーデツド
（コネチカツト州ウオターベリー）の“PLADD”
法を用いて調製した。加工品を塩酸浴中に入れ、
アルミニウム被覆を溶解し、無電解メツキを受け
ることができるように活性化された樹脂表面を出
す。完全にすすいだ後、加工品を触媒処理する。
之は市販型の混合パラジウム・錫触媒を用いた一
段階法で達成することができる。そのような触媒
は、その使用法と共に米国特許第3352518号に記
載されている。すすいだ後、触媒処理された加工
品をいわゆる「促進溶液」中に入れ、表面に残つ
ていた残留錫を減少或は除去する。この場合にも
多くの促進浴を用いることができ、例えば上記特
許第3352518号に記載されているようなものを用
いることができるが、そのような促進浴は一般に
酸溶液からなつている。水酸化ナトリウム溶液の
如きアルカリ性促進剤を用いても成功している。
次に加工品を更にすすいだ後直ぐに銅メツキする
ことができる。
触媒処理した加工品は、次の組成を含む銅浴中
で準付加法を用いて銅メツキした。
CuCl2・2H2O
KNa酒石酸塩・4H2O
NaOH
NAH2PO2・H2O
及び CoCl2・6H2O か又は
NiSO4・6H2O
組成の或る因子及び時間を変化させて得られた結
果を表に示す。表には得られたメツキの厚さを
マイクロセンチ（及びマイクロインチ）で示す。
成分の濃度はモル／である。観察された結果は
次の通りである。
The present invention relates to electroless plating of copper and provides certain improvements over the invention described in commonly assigned U.S. Pat. No. 4,209,331, filed May 25, 1978. In particular, the present invention uses a non-formaldehyde type reducing agent to reduce copper ions dissolved in a solution to metallic copper in the presence of nickel or cobalt ions on a suitably prepared substrate in contact with the solution. The present invention relates to electroless plating of copper in which a metal deposit or coating is formed as a continuous plating process with a desired thickness greater than the limited thicknesses previously available. As used herein, the term electroless plating refers to a plating operation in which the plating thickness increases over time at substantially the same rate as the initial plating rate. The above-mentioned U.S. Pat. No. 4,209,331 describes an invention in which a non-formaldehyde type reducing agent can be suitably used as a copper ion reducing agent in an electroless plating bath in a commercial facility. Certain limitations have been observed in producing conductive metal deposits or coatings on prepared substrates, particularly catalyzed non-conductive substrates. Particularly useful among the reducing agents mentioned are hypophosphites. The present invention uses such a non-formaldehyde type reducing agent system to provide continuously plated metallic copper of a desired thickness by including nickel or cobalt ions as an autocatalyst in the plating bath solution. . Prior Art The description of the prior art contained in the above-mentioned U.S. Pat. Conventional electroless plating, as practiced in the United States, almost exclusively uses highly alkaline formaldehyde solutions of divalent copper ions complexed with well-known chemicals such as Rothsiel's salts, amines, etc. It shows.
Based on the prior art teachings and experience discussed therein, non-formaldehyde type reducing agents such as hypophosphites can successfully reduce copper ions to metallic copper in electroless plating; However, it was unexpected and completely surprising that it could provide benefits not available with typical formaldehyde systems. Although the technical literature clearly shows that hypophosphite agents are effective and widely used as reducing agents in the electroless Nickelmecki process, hypophosphite in the nickel bath can be substituted for formaldehyde in the copper bath. The prior art does not suggest that it can be used. For example, when a prior patent describes both an electroless nickel bath and a copper bath, the bath composition always uses a formaldehyde-type reducing agent for the copper formulation, whereas for the nickel formulation the bath composition always uses a formaldehyde-type reducing agent. Hypophosphite is used for this purpose. Recent US Pat. No. 4,036,651 teaches incorporating sodium hypophosphite as a "plating rate modifier" into alkaline formaldehyde-type electroless copper solutions. The patent states: ``Although sodium hypophosphite is itself a reducing agent in nickel, cobalt, palladium, and silver electroless plating baths, it is a satisfactory reducing agent when used alone in alkaline electroless copper plating baths. is not (i.e.
does not reduce Cu ++ to Cu 0 ).
Where the patent discusses the bath described,
They state that sodium hypophosphite is not used up in the Metski reaction, but instead appears to act as a catalyst for formaldehyde reduction. U.S. Pat. No. 3,716,462 discloses applying an electroless plating solution on zinc or zinc alloy objects consisting essentially of a soluble copper salt such as copper sulfate, a complexing agent such as citric acid, and a reducing agent such as sodium hypophosphite. It is stated that copper coatings can be formed. However, the patent states that ``it has been considered difficult and impracticable to apply electroless copper plating to zinc or its alloys; This contradicts the accepted common wisdom of plating by immersion in a solution.Furthermore, the patent is limited to the plating of zinc;
is generally considered to refer to the deposition of a metal coating onto a generally non-conductive substrate. Furthermore, the hypophosphite present in the solution of that patent does not appear to be of any real use in the described Metzki process. SUMMARY OF THE INVENTION The present invention not only overcomes the shortcomings associated with alkaline formaldehyde-type reducing agent solutions for electroless copper deposition, but also provides a method for depositing copper in larger thicknesses than previously obtained using non-formaldehyde-type reducing agent copper plating solutions. This gives the advantage of being able to obtain deposits with a thickness of . That is, the present invention provides for the continuous plating of metallic copper at a substantially constant rate equal to the initial plating rate when using an electroless copper plating bath with a non-formaldehyde type reducing agent. This is accomplished according to the invention by providing an electroless copper plating bath containing metal ions other than copper, particularly nickel or cobalt ions, in addition to the non-formaldehyde type reducing agent. The present invention thus provides not only the fundamental advantages of the electroless copper bath system with the novel non-formaldehyde reducing agent described in U.S. Pat. It also provides the further surprising and unexpected major advantage of maintaining a more linear deposition rate, rather than producing thicker deposits. Nickel or cobalt ions have synergistic properties in non-formaldehyde reducing systems to produce continuous plating. Ultimately, the electroless copper bath composition and plating process of the present invention allows for thicker deposits to be obtained using non-formaldehyde reduced copper plating systems, affording a broader range of applications on a commercial scale. It has been discovered that different benefits can be obtained using different components in electroless copper plating baths. For example, an electroless copper plating bath using the composition of the present invention may include, in addition to the conventional components that provide a source of cupric ions and their solvent, a non-formaldehyde-type reducing agent,
Advantageously, it comprises a source of hypophosphite, cobalt or nickel ions and a complexing agent or mixture thereof selected to have advantageous compatibility with the nickel or cobalt ions. Complexing agents or mixtures thereof advantageously used in the present invention include those that enable nickel or cobalt to eutectoid with copper. I don't want to be bound by a particular theory, but complexing agents meet these conditions because
the stability constant of nickel or cobalt in solutions containing those agents is substantially the same as that of copper;
It is theorized that this is the case when the same kinetic driving force is obtained. Similarly, although we do not wish to be bound to any particular theory of what is going on, what we are talking about here is that the reduction potential for both the autocatalytic promoter metal and the dissolved copper is essentially the same and the eutectoid This means that it is possible to cause It is anticipated that various complexing agents or mixtures thereof will meet the desired properties described above, specific examples of which include various hydroxy acids and their metal salts such as tartrates, gluconates, glycerol, etc. acid salt,
Contains lactate, etc. Still others may work successfully under controlled conditions. They include amine-type complexing agents such as N-hydroxyethyl ethylenediamine triacetic acid (HEEDTA),
Includes ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) and their alkali metal salts. The metal bath system may optionally contain unsaturated organic compound additives, such as butene diol or butene diol, alkyl sulfonic acids,
Sodium, and Polyox (polyoxyethylene oxide manufactured by Union Carbide), Pluronic 77 (BASF
Polyoxyethylene-polyoxypropylene block copolymer (manufactured by Myandotte Chemical Co.) may also be included. Electroless copper baths containing cobalt or nickel ions are maintained at alkaline conditions. The pH should generally be maintained at a level of at least 7 or higher, preferably in the range 11-14, to give optimal results. This is because at lower pH levels the system tends to become discontinuous, ie, can only be plated up to a limited thickness, which is often too restrictive. As will be explained in more detail below, the properties of the plating bath and process factors such as bath stability, deposition rate and deposit purity can be controlled by the appropriate selection of the above-mentioned components and adjustment of their relative amounts. It is advantageous to decide. Accordingly, one aspect of the present invention is to provide an electroless copper plating bath containing nickel or cobalt ions and free of formaldehyde. Another aspect of the invention is to provide a method for continuously plating copper using a formaldehyde-free electroless copper plating bath. Yet another aspect of the present invention is to provide a formaldehyde-free copper bath system with metal ions other than copper, such that those ions or the resulting precipitates by their presence act as catalysts for continuous copper deposition. The object of the present invention is to provide an electroless copper plating bath composition and a plating method for essentially continuous plating of metallic copper using the system. The foregoing and other aspects and advantages and objects of the invention will become more apparent from the following description of preferred embodiments thereof. Preferred Embodiments Plating solutions having the composition of the present invention contain, in addition to the main components of conventional electroless copper baths, such as a solvent, usually water, and a source of cupric ions, a complexing agent, a non-formaldehyde type reducing agent. , in this case containing a soluble source of hypophosphite and a source of nickel or cobalt ions and, if necessary, a pH regulator. The copper, nickel and cobalt sources in the plating solution can be any of the commonly used soluble salts of these metals. Although chloride and sulfate are usually preferred due to their ready availability, other organic or inorganic anions can also be used. Proper pH level of the plating bath is important to obtain continuous plating, but pH adjustment may be necessary to maintain alkaline conditions. If adjustment is necessary, additional standard acids or bases may be used to bring the value back into the correct operating range. As acidic plating continues to precipitate, the pH of the bath decreases over time, so for long periods of use, it is especially important to
It will be necessary to keep it in the 11-14 range. Usually a caustic substance such as sodium hydroxide is added. Buffers may be used to aid in maintaining the selected pH range. Satisfactory continuous deposits according to the invention are obtained by using as a substrate a suitably prepared surface. That is, the non-conductive base material is
It has a catalyzed surface with a palladium-tin catalyst known in the art. In the system described here, the mechanism by which copper ions are continuously reduced to copper metal in the presence of cobalt or nickel ions is unknown.
However, the following hypothesis can be considered. A noble metal catalyst such as palladium on the surface of the substrate
The reaction is initiated by forming strong reducing radicals or radical ions from the hypophosphite reducing agent. These strongly reducing substances on the surface of the catalyst serve to reduce copper ions to copper metal through an electron transfer reaction. It is believed that as the copper metal is reduced, small amounts of dissolved cobalt or nickel are also reduced and are included in small amounts in the copper deposit as nickel metal or cobalt metal or some copper-cobalt or copper-nickel alloys. Examination of the deposited metals reveals that small amounts of cobalt or nickel are present in the copper deposits. As deposition progresses, the palladium precious metal catalyst is eventually coated and the included cobalt or nickel metal, or cobalt-copper or nickel-copper alloy, further reacts with the hypophosphite reducing agent and the electroless plating process continues. It is believed that the reducing radicals or radical ions necessary for this purpose are generated. Sodium hypophosphite is the most readily available form of hypophosphite and is therefore preferred. Hypophosphorous acid is also available and the pH value for preparing baths of this material is
Can be used with modifiers. The optimum concentration is one sufficient to form a suitable copper coating within a reasonable amount of time. The type of complexing agent used will to some extent affect the plating rate as well as the continuity of the plating and the type of deposit obtained. For example, if cobalt is the autocatalytic promoter ion in a hypophosphite-reduced copper bath, complexing agents such as tartrate, gluconate, and trihydroxyglutaric acid are advantageous for continuous plating of thin coatings. . When using alkylamine complexing agents such as N-hydroxyethyl ethylenediamine triacetic acid (HEEDTA), ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), copper bath systems containing nickel or cobalt ions may be continuous if the amount of complexing agent added is insufficient to trap all the nickel or cobalt ions.
That is, some nickel and cobalt ions must be free to eutectoid to maintain a continuous plating process. Nickel and cobalt will react if the complexing agent is too strong.
That is, promoting the stabilization of the oxidation state to a higher degree prevents eutectoid deposition. The balance of such complexing agents in the system must therefore be controlled in order to perform continuous plating. In addition to the above complexing agents, unsaturated organic compounds, polymers, and combinations thereof may also be successfully added. Optional additives such as butyne or butenediol, sodium alkyl sulfonates and polymers such as Polyox and Pluronic 77 are compatible with the system of the invention and have an effect similar to that known in electroplating systems. It will affect you there. It has been observed that the rate of copper deposition from electroless solutions is essentially linear. For example, plating was still progressing after 90 minutes, indicating that precipitation was continuing for a longer period of time. It is certain that by such time the palladium on the catalyzed surface has been coated with precipitates and no longer acts as an active catalyst for the continuous plating operation. . Although this system appears to be inert towards pure copper, it can be solved in various ways by suitably catalyzing the surface to solve the ultimate passivation, and As a result, electroless plating occurs. The following examples illustrate preferred conditions for practicing the invention. Examples 1-18 In these examples, “Epoxglass FR-4
A U.S. patent describes a fabricated article of plastic substrate originally in the form of a laminate material consisting of aluminum foil bonded to a fiberglass-reinforced epoxy resin substrate known commercially as ``PLADD Laminate.'' “PLADD” of McDiarmid Inc., Waterbury, Conn. No. 3620933.
prepared using the method. Place the processed product in a hydrochloric acid bath,
The aluminum coating is melted to reveal an activated resin surface capable of undergoing electroless plating. After thorough rinsing, the workpiece is catalyzed.
This can be accomplished in a one-step process using a commercially available mixed palladium-tin catalyst. Such catalysts are described in US Pat. No. 3,352,518, along with their use. After rinsing, the catalytically treated workpiece is placed in a so-called "promoting solution" to reduce or remove any residual tin left on the surface. Again, many promoting baths can be used, such as those described in Patent No. 3,352,518 mentioned above, but such promoting baths generally consist of acid solutions. Alkaline promoters such as sodium hydroxide solution have also been used with success.
The workpiece can then be further rinsed and then immediately copper plated. The catalyzed workpiece was copper plated using a quasi-additive method in a copper bath containing the following composition: CuCl 2.2H 2 O KNa tartrate 4H 2 O NaOH NAH 2 PO 2.H 2 O and CoCl 2.6H 2 O or NiSO 4.6H 2 O obtained by varying certain factors of composition and time. The results are shown in the table. The table shows the thickness of the plating obtained in microcentimeters (and microinches).
The concentration of the components is in mol/. The observed results are as follows.
【表】【table】
【表】
実施例１、２及び３は10、30及び60の浸漬時間
で、ニツケル或はコバルト自触媒反応促進剤を含
まない浴配合を示している。メツキの厚さは約
38.1μcm（15μin）迄大きくなつたがそこで止まつ
た。メツキ時間を長くしても付着物の厚さは増加
する結果にならないことが分る。メツキが止まつ
た後で銅表面に或る種の酸化物が発生する。
実施例４、５及び６は実施例１、２及び３のく
り返しであるが、但し少量のコバルトイオンが浴
組成に添加されている。付着物はピンク色で導電
性及び基材への接着が良好であることを示してい
た。メツキの停止は起きず、付着速度の直線性が
浸漬時間が長くなつても見られた。
実施例７、８及び９は種々のイオン濃度の効果
を示し、コバルトイオン濃度が高いとメツキ速度
を促進するように見える。
実施例10、11及び12はコバルトイオンの代りに
ニツケルイオンを用いた時のメツキ速度の直線性
を示している。
実施例13、14及び15は、ニツケルイオン水準を
変えた時の結果を示している。ニツケルイオン濃
度が高くなつても、コバルトイオンの場合に見ら
れた程メツキ速度を激的に促進することはないよ
うに見える。
実施例16、17及び18は温度を変えた時の効果を
示している。一般に予想される如く、温度が高く
なる程、大きな付着速度を与える。
実施例 19−22
銅メツキを実施例１−18の手順に従つて実施例
19−22で行なつた。但し酒石酸の代りに錯化剤と
してグリコン酸ナトリウムへ中和したグルコン酸
を用いた。結果を第表に示す。TABLE Examples 1, 2, and 3 represent bath formulations with soak times of 10, 30, and 60 and without nickel or cobalt autocatalytic promoters. The thickness of the mesh is approx.
It grew to 38.1μcm (15μin) but stopped there. It can be seen that increasing the plating time does not result in an increase in the thickness of the deposit. After plating has stopped, some oxides are generated on the copper surface. Examples 4, 5 and 6 are repeats of Examples 1, 2 and 3, except that a small amount of cobalt ion is added to the bath composition. The deposit was pink, indicating good conductivity and adhesion to the substrate. No plating stalling occurred and linearity of deposition rate was observed even with increasing soak time. Examples 7, 8 and 9 show the effect of various ion concentrations, with higher cobalt ion concentrations appearing to promote plating rate. Examples 10, 11 and 12 demonstrate the linearity of plating rate when nickel ions are used in place of cobalt ions. Examples 13, 14 and 15 show the results when varying the nickel ion level. Higher concentrations of nickel ions do not appear to accelerate the plating rate as drastically as was seen with cobalt ions. Examples 16, 17 and 18 show the effect of varying temperature. As is generally expected, higher temperatures give greater deposition rates. Example 19-22 Copper plating was carried out according to the procedure of Example 1-18.
It was held on 19-22. However, instead of tartaric acid, gluconic acid neutralized to sodium glyconate was used as a complexing agent. The results are shown in Table 1.
【表】
実施例19はニツケル或はコバルトイオンの自触
媒反応促進剤は含んでおらず、約38.1μcm
（15μin）でメツキが止つたことを示している。
実施例20はニツケルイオンの添加がこの浴の自
触媒反応性を促進することを示している。
実施例21及び22は、有機重合体ポリエチレン
グリコール（P.E.G−20000分子量）を添加した
効果を例示している。その材料100ppmを添加す
るとメツキ速度が低下する。しかし、この系の自
触媒反応性及びメツキ速度の直線性は維持され
る。ポリエチレングリコールを添加すると、メツ
キ速度を低下するが、一層ピンク色で滑らかな付
着物を与えるように見え、然も溶液に安定性が加
わる。
実施例 23−35
実施例23−35は前の実施例のメツキ手順を用い
て得られた結果を示しているが、成分濃度を変
え、不飽和有機又は重合体添加物を用いている。
結果を表に示す。
実施例23と24はBASF Wyandotte Chemical
Co製のポリオキシエチレン ポリオキシエチレ
ン ブロツク共重合体であるプルロニツク 77を
250ppm用いている。時間はメツキ速度の直線性
が示されるように変えた。プルロニツク 77は一
層ピンク色で滑らかな付着物を与え、溶液の安定
性が増大するように見えた。
実施例25と26は有機添加剤としてブチンジオー
ルを100ppm使用した。この場合も析出速度の直
線性が維持され、ブチンジオールは一層ピンク色
で滑らかな付着物を与え、浴の安定性が増すよう
に見えた。
実施例27、28、29及び30は有機添加物ブチンジ
オールの濃度を０〜500ppm迄変えた効果を示し
ている。これらの実施例はブチンジオールを添加
すると付着速度を遅くし、ブチンジオールの濃度
を増大するとそれに応じて一層低い付着速度を与
えることを例示している。有機添加物によつて起
されるメツキ速度の低下に伴つて、いくらか一層
滑らかで一層ピンク色の付着物になることが明ら
かであり、溶液の安定性は増大する。
実施例31−35は自触媒反応促進剤としてニツケ
ルイオンを、有機添加物としてポリエチレングリ
コール（P.E.G）を用いている。P.E.Gの濃度を
増大することによつて、メツキ速度が低下し、一
層ピンク色で一層滑らかな付着物を与えるように
見える点で、、同様な傾向が観察された。[Table] Example 19 does not contain nickel or cobalt ion autocatalytic reaction accelerator, and has approximately 38.1 μcm
(15 μin) indicates that the plating stopped. Example 20 shows that the addition of nickel ions promotes the autocatalytic reactivity of this bath. Examples 21 and 22 are organic polymer polyethylene
The effect of adding glycol (PEG-20000 molecular weight) is illustrated. Adding 100 ppm of that material reduces the plating speed. However, the autocatalytic reactivity and plating rate linearity of this system are maintained. Adding polyethylene glycol slows down the plating rate but appears to give a pinker, smoother deposit while adding stability to the solution. Examples 23-35 Examples 23-35 show the results obtained using the plating procedure of the previous example, but varying the component concentrations and using unsaturated organic or polymeric additives.
The results are shown in the table. Examples 23 and 24 are BASF Wyandotte Chemical
Pluronic 77, a polyoxyethylene block copolymer made from Co.
250ppm is used. Time was varied to demonstrate linearity of plating rate. Pluronik 77 gave a pinker, smoother deposit and appeared to increase the stability of the solution. Examples 25 and 26 used 100 ppm of butynediol as an organic additive. Again, the linearity of the deposition rate was maintained, the butyne diol gave a pinker, smoother deposit, and bath stability appeared to be increased. Examples 27, 28, 29 and 30 show the effect of varying the concentration of the organic additive butynediol from 0 to 500 ppm. These examples illustrate that adding butyne diol slows the deposition rate and increasing the concentration of butyne diol provides a correspondingly lower deposition rate. With the reduction in plating rate caused by the organic additive, a somewhat smoother and pinker deposit is evident, and the stability of the solution increases. Examples 31 to 35 use nickel ions as an autocatalytic reaction promoter and polyethylene glycol (PEG) as an organic additive. A similar trend was observed in that increasing the concentration of PEG appeared to decrease the plating rate and give a pinker and smoother deposit.
【表】【table】
【表】
実施例 36−37
実施例36及び37は前の実施例と同様であるが、
但しメツキ浴はアミノ酸錯化剤のニトリロ三酢酸
（NTA）、及びヒドロキシ酸錯化剤の酒石酸を用
いた。表に記載した結果は、この系でも付着速
度の直線性が維持されていることを示している。[Table] Examples 36-37 Examples 36 and 37 are similar to the previous examples, but
However, the methane bath used nitrilotriacetic acid (NTA), an amino acid complexing agent, and tartaric acid, a hydroxy acid complexing agent. The results listed in the table show that the linearity of the deposition rate is maintained in this system.
【表】
実施例 38−46
実施例38−46では市販のメツキ用標準ABSパ
ネルからなる典型的な加工品を先ず洗滌し、表面
のよごれ、油等を除いた。従来のメツキ系で典型
的に用いられていたアルカリ性洗滌溶液をここで
も用いた。次に工業薬品として標準的な混合クロ
ム・硫酸又はクロム酸単独を用いて化学的にエツ
チングした。典型的な処理条件である濃度及び処
理時間は米国特許第3515649号に記載されている。
加工品を次に前の実施例で記載したようなすす
ぎ、触媒処理及び促進浴といつた典型的なメツキ
前処理操作にかけた。次に加工品を種々のメツキ
浴中に浸漬した。結果を表に示す。表にはメツ
キの付着が止まつた時間（分）が示されている。
mg／cm2で表した被覆重量も示されている。[Table] Examples 38-46 In Examples 38-46, a typical processed product consisting of a commercially available standard ABS panel for plating was first washed to remove surface dirt, oil, etc. The alkaline cleaning solution typically used in conventional plating systems was also used here. Next, chemical etching was performed using a standard industrial chemical mixture of chromium and sulfuric acid or chromic acid alone. Typical processing conditions, concentrations and processing times are described in US Pat. No. 3,515,649.
The workpiece was then subjected to typical plating pretreatment operations such as rinsing, catalyzing, and promoting baths as described in previous examples. The workpieces were then immersed in various plating baths. The results are shown in the table. The table shows the time (in minutes) when plating stopped adhering.
The coating weight in mg/cm 2 is also shown.
【表】
実施例38はニツケル又はコバルトイオン自触媒
反応促進剤を含んでいないメツキ浴を例示してい
る。ABS加工品は典型的なメツキ前処理が行わ
れているが、表に記載の条件でメツキを得るこ
とが可能である。
実施例39、40及び41は浴中のコバルトイオンの
効果を示す実施例を示している。表の例は、一
定の浴配合物中でのコバルト又はニツケルイオン
の如き自触媒反応促進剤金属の濃度を増大した場
合の効果を例示している。メツキの付着が止つた
大体の時間はガスの発生（水素ガス発生）が止つ
たのを観察することにより明らかになる。亦、変
色（或る種の酸化物が形成されたものと思われ
る）が付着金属に起きた。この現象ではここでは
メツキが止まつたものとして言及されている。
之等の試験中、浴の成分は補充しなかつたの
で、自触媒反応促進剤金属が溶液から実際上なく
なると直ちに無電解メツキが止まるものと推測さ
れた。このことはコバルトイオンの濃度を増大す
ると一層長い時間無電解メツキが続くようにな
り、一層大きな厚みに成長するようになることを
示している実施例39−41から明らかである。実施
例42−46はニツケルイオンについての同様な効果
を示している。両方の場合に対し、もし必須成分
のメツキに有効な濃度を維持するように補充した
ならば、無電解メツキ工程は終ることなく継続す
ることに注意すべきである。
実施例 47−52
実施例47−52は実施例38−46に記載したABS
加工品をメツキすることに関する。メツキ浴の浸
漬時間及び温度を変えた時の結果は表に示され
ている。TABLE Example 38 illustrates a plating bath that does not contain a nickel or cobalt ion autocatalytic reaction promoter. ABS processed products undergo typical plating pretreatment, but plating can be obtained under the conditions listed in the table. Examples 39, 40 and 41 provide examples that demonstrate the effect of cobalt ions in the bath. The example table illustrates the effect of increasing the concentration of autocatalytic promoter metals, such as cobalt or nickel ions, in a given bath formulation. The approximate time it takes for plating to stop adhering can be determined by observing when gas generation (hydrogen gas generation) stops. Additionally, discoloration (possibly due to the formation of some type of oxide) occurred on the deposited metal. This phenomenon is referred to here as the cessation of mitsuki. Because the bath components were not replenished during these tests, it was assumed that electroless plating would cease as soon as the autocatalytic promoter metal was effectively removed from solution. This is evident from Examples 39-41, which show that increasing the concentration of cobalt ions causes electroless plating to last longer and grow to greater thicknesses. Examples 42-46 show similar effects for nickel ions. It should be noted that in both cases, if the essential components are replenished to maintain plating-effective concentrations, the electroless plating process will continue indefinitely. Example 47-52 Example 47-52 is the ABS described in Example 38-46.
Concerning plating processed products. The results of varying the immersion time and temperature of the plating bath are shown in the table.
【表】
実施例47、48及び49は付着速度の直線性を示し
ている。浸漬時間が増大するにつれて、効果的に
比例即ち直線的速度で付着物の厚みが増大する。
実施例50、51及び52は、与えられた浸漬時間に
対し、付着物の厚みが温度を上げると増加するこ
とを示している。
之等全ての実施例に於て、付着物は滑らかでピ
ンク色であり、基材によく付着しており、後の電
解メツキに対し直ちに使用できるものであつた。
基材に付着した金属の典型的な量は約8Ib/inであ
つた。
実施例 53−57
実施例53−57は基本成分の濃度水準を変てもう
まくいくことを例示している。表に示した結果
は、成分のメツキ可能な限界を狭く設定するので
はなく、反応を行わせるのに最低の量の基本成分
を用いても本発明のメツキ浴は有効に作動するこ
とを示している。
勿論一層多量の材料を用いてもよいが、最大量
の決定は基本成分が互に及ぼす種々の相乗効果を
観察することによつて最もよく行うことができ
る。一般的な指針は溶解度を越えるような種々の
成分の濃度を避けることであろう。亦、最大溶解
度水準に近い所での操作は、それを保持するため
の添加の余地が残つておらず、正常な操作中での
還元生成物を可溶化する余地も残らないことにな
るであろう。勿論、経済的見地から溶解作業をだ
らだら長びかせることはコストを増加することに
なるので、機能的に不必要な濃度を維持すること
は商業的に実際的ではないであろう。当業者であ
れば得られた結果を単に観察することにより適切
な水準を確かめることができ、特定の目的に合つ
たようにそれらの水準を変えることができるであ
ろう。Table: Examples 47, 48 and 49 demonstrate linearity in deposition rate. As the soak time increases, the deposit thickness increases at an effectively proportional or linear rate. Examples 50, 51 and 52 show that for a given soaking time, the deposit thickness increases with increasing temperature. In all of these examples, the deposits were smooth, pink in color, adhered well to the substrate, and were ready for subsequent electrolytic plating.
The typical amount of metal deposited on the substrate was about 8 Ib/in. Examples 53-57 Examples 53-57 illustrate the success of varying the concentration levels of the base ingredients. The results shown in the table demonstrate that the plating bath of the present invention operates effectively even when using the lowest amount of the basic component to effect the reaction, rather than setting narrow limits to which components can be plated. ing. Of course, larger amounts of the materials may be used, but the maximum amount is best determined by observing the various synergistic effects that the basic components have on each other. A general guideline would be to avoid concentrations of the various components that exceed their solubility. Additionally, operating near the maximum solubility level will leave no room for addition to maintain it and no room to solubilize the reduction product during normal operation. Dew. Of course, from an economic standpoint it would be commercially impractical to maintain functionally unnecessary concentrations since prolonged dissolution operations would increase costs. Those skilled in the art will be able to ascertain appropriate levels simply by observing the results obtained and will be able to vary these levels to suit particular purposes.
【表】
上記の“Epoxyglass FR−４ PLADD
Laminate”の無電解メツキが成功していること
は、プリント回路板を調製するのに用いられる準
付加メツキ法に対し、本発明が適合していること
を示している。薄い銅メツキ物を基板の表面に亘
つて無電解的に付着させた後、マスク又はレジス
トを適用し、スクリーン法、光重合法による現像
等々により希望のプリント回路を定める。マスク
された（薄くメツキされた）基板を次に母線の如
き最初の無電解メツキ物を用いて電解浴中でメツ
キし、回路板のマスクされていない領域に更に或
る厚さに金属を付着させる。レジスト或はマスク
を次に化学的に溶解し、その板を例えば米国特許
第3466208号に記載の如き適当な銅エツチング溶
液中に入れ、レジストによつて前に被覆されてい
た最初の薄い銅付着物を除去するには充分である
が、電解メツキ浴で蓄積した銅（又は他の金属）
付着物の実質的に一層厚い部分を除去するには不
充分な時間保持する。この方法は時々準付加
（semi−additive）メツキ法として当分野では言
及されている。
同様なやり方で本発明は、標準の銅箔被覆積層
体の両面にある導電体域を相互に結合するための
貫通孔を有するプリント回路板を製造するための
減法（subtractive procedure）にも適用できる。
回路板素材に貫通孔をパンチ又はドリルであけ、
本発明の銅溶液を用いてそれらの貫通孔の壁を無
電解的に銅でメツキする。次に希望の回路網が得
られるようにレジストを適用し、もし望むなら回
路網と同様それらの壁にも或る厚さの付着物を電
解メツキで形成することができる。回路上の接続
端子域の金メツキ、はんだ被覆等々の如き更に別
のメツキ条件により、回路板を次にエツチング浴
に入れて最初の箔の非回路域を除去する。
本発明の特定の具体例について今迄詳述してき
たが、それらは本来例示の為であることを理解す
べきである。当業者には明らかなように、ここで
教示した事に基いて記載の特定の条件及び成分を
特別な要件に適合するように変えることもでき
る。[Table] “Epoxyglass FR-4 PLADD” above
The success of electroless plating of "laminate" demonstrates the suitability of the present invention for semi-additive plating methods used to prepare printed circuit boards. After electroless deposition over the surface of the substrate, a mask or resist is applied and the desired printed circuit is defined by screening, photopolymerization, etc. The masked (thinly plated) substrate is then The first electroless plating material, such as a busbar, is plated in an electrolytic bath to deposit additional metal to the unmasked areas of the circuit board to a certain thickness.The resist or mask is then chemically plated. Dissolving and placing the plate in a suitable copper etching solution, such as that described in U.S. Pat. No. 3,466,208, is sufficient to remove the initial thin copper deposit previously covered by the resist. , copper (or other metals) accumulated in electrolytic plating baths
Hold for an insufficient time to remove substantially thicker portions of the deposit. This method is sometimes referred to in the art as a semi-additive plating method. In a similar manner, the invention can also be applied to a subtractive procedure for manufacturing printed circuit boards with through holes for interconnecting conductive areas on both sides of a standard copper foil-clad laminate. .
Punch or drill a through hole in the circuit board material,
The walls of the through holes are electrolessly plated with copper using the copper solution of the invention. A resist is then applied to obtain the desired network, and if desired, the walls as well as the network can be electrolytically plated to a certain thickness. Due to further plating conditions such as gold plating, solder coating, etc. of the connection terminal areas on the circuit, the circuit board is then placed in an etching bath to remove the non-circuit areas of the initial foil. Although specific embodiments of the invention have been described in detail, it is to be understood that they are exemplary in nature. Those skilled in the art will recognize that, based on the teachings herein, the specific conditions and components described may be modified to suit particular requirements.
Claims (1)
二銅イオンを溶解状態に維持するための錯化剤、
可溶性次亜燐酸イオン源及び可溶性のコバルト及
び／又はニツケルイオン源からなり、第二銅イオ
ン対コバルト及び／又はニツケルイオンのモル比
が少なくとも5.5：１、組成物のpHが11〜14であ
る、無電解銅メツキ組成物。 ２ 錯化剤は、溶液中で第二銅イオン以外の金属
イオンが、少量で第二銅イオンと一緒に付着して
本質的に銅の付着物を形成できる錯化剤である特
許請求の範囲第１項に記載の組成物。 ３ 錯化剤が、第二銅イオンの安定定数に実質的
に等しい安定定数をもつて第二銅イオン以外の金
属イオンを与え、溶液中の全ての金属イオンに対
し実質的に同じ反応速度の推進力を与えることが
できる錯化剤である、前記第２項に記載の組成
物。 ４ 錯化剤が可溶性ヒドロキシ酸とヒドロキシ酸
金属塩からなる群から選択された錯化剤である前
記第１項に記載の無電解銅メツキ組成物。 ５ 錯化剤が可溶性の酒石酸塩、グルコン酸塩、
グリセリン酸塩、グリコール酸塩、乳酸塩及びそ
れらの混合物からなる群から選ばれた錯化剤であ
る前記第１項に記載の無電解銅メツキ組成物。 ６ 錯化剤が更に、Ｎ―ヒドロキシエチル エチ
レンジアミン 三酢酸（HEEDTA）、エチレン
ジアミン四酢酸（EDTA）及びニトリロ三酢酸
（NTA）及びそれらのアルカリ金属塩からなる
群から選択されたアミノ酸錯化剤からなる前記第
１項に記載の無電解銅メツキ組成物。 ７ 錯化剤がＮ―ヒドロキシエチル エチレンジ
アミン 三酢酸（HEEDTA）、エチレンジアミ
ン四酢酸（EDTA）及びニトリロ三酢酸
（NTA）からなる群から選択された錯化剤であ
り、然も非第三銅イオンの全てと反応してそれと
の錯化物を形成するには不充分な量で存在し、従
つて少なくともいくらかの非第二銅イオンが残留
していて銅と一緒に付着することができる前記第
１項に記載の無電解銅メツキ組成物。 ８ 不飽和有機化合物と重合体からなる群から選
択された添加化合物を更に含有する前記第１項に
記載の無電解銅メツキ組成物。 ９ 添加化合物はブチンジオール、ブテンジオー
ル、ポリオキシエチレン、ポリエチレングリコー
ル及びポリオキシエチレンとポリオキシプロピレ
ンとのブロツク共重合体からなる群から選択され
る前記第８項に記載の無電解銅メツキ組成物。[Claims] 1. An aqueous solution containing a source of soluble cupric ions, a complexing agent for maintaining the cupric ions in a dissolved state,
comprising a source of soluble hypophosphite ions and a source of soluble cobalt and/or nickel ions, wherein the molar ratio of cupric ions to cobalt and/or nickel ions is at least 5.5:1, and the pH of the composition is between 11 and 14; Electroless copper plating composition. 2. The claim that the complexing agent is a complexing agent that allows metal ions other than cupric ions to adhere together with cupric ions in small amounts in solution to form deposits that are essentially copper. Composition according to item 1. 3. The complexing agent provides metal ions other than cupric ions with a stability constant substantially equal to the stability constant of cupric ions, and provides substantially the same reaction rate for all metal ions in the solution. The composition according to item 2 above, which is a complexing agent capable of providing a driving force. 4. The electroless copper plating composition according to item 1 above, wherein the complexing agent is selected from the group consisting of soluble hydroxy acids and hydroxy acid metal salts. 5 tartrate, gluconate, in which the complexing agent is soluble;
2. The electroless copper plating composition of item 1, wherein the complexing agent is selected from the group consisting of glycerates, glycolates, lactates, and mixtures thereof. 6. The complexing agent further comprises an amino acid complexing agent selected from the group consisting of N-hydroxyethyl ethylenediamine triacetic acid (HEEDTA), ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) and their alkali metal salts. The electroless copper plating composition according to item 1 above. 7. The complexing agent is a complexing agent selected from the group consisting of N-hydroxyethyl ethylenediamine triacetic acid (HEEDTA), ethylenediaminetetraacetic acid (EDTA), and nitrilotriacetic acid (NTA), and also contains non-cupric ions. said first term, which is present in an insufficient amount to react with and form complexes with all of the copper, such that at least some non-cupric ions remain and can be deposited with the copper. The electroless copper plating composition described in . 8. The electroless copper plating composition according to item 1, further comprising an additive compound selected from the group consisting of unsaturated organic compounds and polymers. 9. The electroless copper plating composition according to item 8, wherein the additive compound is selected from the group consisting of butene diol, butene diol, polyoxyethylene, polyethylene glycol, and a block copolymer of polyoxyethylene and polyoxypropylene. .
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/964,128 US4265943A (en) | 1978-11-27 | 1978-11-27 | Method and composition for continuous electroless copper deposition using a hypophosphite reducing agent in the presence of cobalt or nickel ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5576054A JPS5576054A (en) | 1980-06-07 |
| JPS6344822B2 true JPS6344822B2 (en) | 1988-09-07 |
Family
ID=25508161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13972779A Granted JPS5576054A (en) | 1978-11-27 | 1979-10-29 | Electroless coppur plating composition |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4265943A (en) |
| JP (1) | JPS5576054A (en) |
| AU (1) | AU535517B2 (en) |
| CA (1) | CA1117704A (en) |
| CH (1) | CH649580A5 (en) |
| DE (1) | DE2947306A1 (en) |
| FR (1) | FR2442278B2 (en) |
| GB (1) | GB2037327B (en) |
| NL (1) | NL188173C (en) |
| SE (1) | SE463820B (en) |
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| US3046159A (en) * | 1957-12-17 | 1962-07-24 | Hughes Aircraft Co | Method of copper plating by chemical reduction |
| US3093509A (en) * | 1959-09-28 | 1963-06-11 | Wein Samuel | Process for making copper films |
| US3352518A (en) * | 1965-10-23 | 1967-11-14 | Kidde & Co Walter | Personnel ejection system for aircraft |
| US3615735A (en) * | 1968-08-13 | 1971-10-26 | Shipley Co | Electroless copper plating |
| US3615733A (en) * | 1968-08-13 | 1971-10-26 | Shipley Co | Electroless copper plating |
| US3615732A (en) * | 1968-08-13 | 1971-10-26 | Shipley Co | Electroless copper plating |
| US3620933A (en) * | 1969-12-31 | 1971-11-16 | Macdermid Inc | Forming plastic parts having surfaces receptive to adherent coatings |
| US3716462A (en) * | 1970-10-05 | 1973-02-13 | D Jensen | Copper plating on zinc and its alloys |
| US3754940A (en) * | 1972-09-06 | 1973-08-28 | Crown City Plating Co | Electroless plating solutions containing sulfamic acid and salts thereof |
| JPS5248580B2 (en) * | 1973-07-21 | 1977-12-10 | ||
| US3935013A (en) * | 1973-11-12 | 1976-01-27 | Eastman Kodak Company | Electroless deposition of a copper-nickel alloy on an imagewise pattern of physically developable metal nuclei |
| US4036651A (en) * | 1974-02-26 | 1977-07-19 | Rca Corporation | Electroless copper plating bath |
| DD109669A1 (en) * | 1974-03-15 | 1974-11-12 | ||
| US4019910A (en) * | 1974-05-24 | 1977-04-26 | The Richardson Chemical Company | Electroless nickel polyalloy plating baths |
| JPS5125432A (en) * | 1974-08-28 | 1976-03-02 | Mitsubishi Gas Chemical Co | MUDENKAIDOMETSUKIHOHO |
| US4048354A (en) * | 1975-10-23 | 1977-09-13 | Nathan Feldstein | Method of preparation and use of novel electroless plating catalysts |
| US4138267A (en) * | 1976-12-28 | 1979-02-06 | Okuno Chemical Industry Company, Limited | Compositions for chemical copper plating |
| US4209331A (en) * | 1978-05-25 | 1980-06-24 | Macdermid Incorporated | Electroless copper composition solution using a hypophosphite reducing agent |
-
1978
- 1978-11-27 US US05/964,128 patent/US4265943A/en not_active Expired - Lifetime
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1979
- 1979-09-05 SE SE7907373A patent/SE463820B/en not_active IP Right Cessation
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- 1979-10-19 CA CA000338071A patent/CA1117704A/en not_active Expired
- 1979-10-29 AU AU52277/79A patent/AU535517B2/en not_active Ceased
- 1979-10-29 JP JP13972779A patent/JPS5576054A/en active Granted
- 1979-11-02 FR FR7927148A patent/FR2442278B2/en not_active Expired
- 1979-11-23 DE DE19792947306 patent/DE2947306A1/en active Granted
- 1979-11-23 CH CH10443/79A patent/CH649580A5/en not_active IP Right Cessation
- 1979-11-27 GB GB7940951A patent/GB2037327B/en not_active Expired
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| NL7907555A (en) | 1980-05-29 |
| NL188173C (en) | 1992-04-16 |
| AU535517B2 (en) | 1984-03-29 |
| US4265943A (en) | 1981-05-05 |
| SE463820B (en) | 1991-01-28 |
| CH649580A5 (en) | 1985-05-31 |
| JPS5576054A (en) | 1980-06-07 |
| CA1117704A (en) | 1982-02-09 |
| NL188173B (en) | 1991-11-18 |
| DE2947306A1 (en) | 1980-06-04 |
| FR2442278B2 (en) | 1985-09-20 |
| GB2037327B (en) | 1983-11-09 |
| GB2037327A (en) | 1980-07-09 |
| SE7907373L (en) | 1980-05-28 |
| DE2947306C2 (en) | 1988-01-21 |
| AU5227779A (en) | 1980-05-29 |
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